US10822243B1 - Molecular sieve SSZ-118, its synthesis and use - Google Patents
Molecular sieve SSZ-118, its synthesis and use Download PDFInfo
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- US10822243B1 US10822243B1 US16/856,126 US202016856126A US10822243B1 US 10822243 B1 US10822243 B1 US 10822243B1 US 202016856126 A US202016856126 A US 202016856126A US 10822243 B1 US10822243 B1 US 10822243B1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 238000003786 synthesis reaction Methods 0.000 title description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 19
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 82
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- 239000012084 conversion product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- -1 hydroxide ions Chemical class 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 238000001144 powder X-ray diffraction data Methods 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000408939 Atalopedes campestris Species 0.000 description 1
- OTQFRBPDKVOCRZ-UHFFFAOYSA-N C[N+]1(CCCCCC[N+]2(C)CCCC2)CCCC1 Chemical compound C[N+]1(CCCCCC[N+]2(C)CCCC2)CCCC1 OTQFRBPDKVOCRZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- This disclosure relates to a novel synthetic crystalline molecular sieve designated SSZ-118, its synthesis, and its use in organic compound conversion and sorption processes.
- Molecular sieves are a commercially important class of materials that have distinct crystal structures with defined pore structures that are shown by distinct X-ray diffraction (XRD) patterns and have specific chemical compositions.
- the crystal structure defines cavities and pores that are characteristic of the specific type of molecular sieve.
- SSZ-118 a new crystalline molecular sieve, designated SSZ-118 and having a unique powder X-ray diffraction pattern, has now been synthesized using 1,6-bis(N-methylpyrrolidinium)hexane dications as a structure directing agent.
- a molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including the following peaks:
- the molecular sieve in its as-synthesized and anhydrous form, can have a chemical composition comprising the following molar relationship:
- a molecular sieve having, in its calcined form, a powder X-ray diffraction pattern including the following peaks:
- the molecular sieve in its calcined form, can have a chemical composition comprising the following molar relationship: Al 2 O 3 :( n )SiO 2 wherein n is in a range of from 20 to 100.
- a method of synthesizing the molecular sieve described herein comprising (a) providing a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve
- a process of converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising the molecular sieve described herein.
- FIG. 1 compares the powder X-ray diffraction (XRD) patterns of as-synthesized SSZ-118 prepared in Example 1, calcined SSZ-118 prepared in Example 7, and zeolite Beta prepared in Example 5.
- XRD powder X-ray diffraction
- FIG. 2 is a Scanning Electron Micrograph (SEM) image of as-synthesized SSZ-118 prepared in Example 1.
- as-synthesized is employed herein to refer to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
- anhydrous is employed herein to refer to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
- Molecular sieve SSZ-118 can be synthesized by: (a) providing a reaction mixture comprising (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane dications; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- a reaction mixture comprising (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane dications; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sie
- the reaction mixture can have a composition, in terms of molar ratios, within the ranges set forth in Table 1:
- the reaction mixture can have a SiO 2 /Al 2 O 3 molar ratio in a range of 60 to 80.
- Suitable sources of silicon oxide can include colloidal silica, fumed silica, precipitated silica, alkali metal silicates and tetraalkyl orthosilicates.
- Suitable sources of aluminum oxide can include hydrated alumina, aluminum hydroxide, alkali metal aluminates, aluminum alkoxides, and water-soluble aluminum salts (e.g., aluminum nitrate).
- Combined sources of silicon oxide and aluminum oxide can additionally or alternatively be used and can include aluminosilicate zeolites (e.g., zeolite Y) and clays or treated clays (e.g., metakaolin).
- zeolites e.g., zeolite Y
- clays or treated clays e.g., metakaolin
- Sources of the Group 1 or Group 2 metal can include metal hydroxide, metal oxide, metal halide, metal sulfate, metal nitrate, metal carboxylate, and metal aluminate.
- Group 1 or Group 2 metal does not mean the Group 1 metals and Group 2 metals are used in the alternative, but instead that one or more Group 1 metals can be used alone or in combination with one or more Group 2 metals and that one or more Group 2 metals can be used alone or in combination with one or more Group 1 metals.
- Preferred Group 1 or Group 2 metals include sodium, potassium, and combinations thereof.
- the structure directing agent (Q) comprises 1,6-bis(N-methylpyrrolidinium)hexane dications, represented by the following structure (1):
- Suitable sources of Q are the hydroxides and/or other salts of the diquaternary ammonium compound.
- the reaction mixture may contain seeds of a crystalline material, such as SSZ-118 from a previous synthesis, in an amount of from 0.01 to 10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) of the reaction mixture. Seeding can be advantageous in decreasing the amount of time necessary for complete crystallization to occur. In addition, seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of SSZ-118 over any undesired phases.
- seeds of a crystalline material such as SSZ-118 from a previous synthesis
- reaction mixture components can be supplied by more than one source. Also, two or more reaction components can be provided by one source.
- the reaction mixture can be prepared either batchwise or continuously.
- Crystallization of the molecular sieve from the above reaction mixture can be carried out under either static, tumbled or stirred conditions in a suitable reactor vessel, such as polypropylene jars or Teflon-lined or stainless-steel autoclaves, at a temperature of from 125° C. to 200° C. (e.g., 150° C. to 180° C.) for a time sufficient for crystallization to occur at the temperature used (e.g., from 1 day to 14 days). Crystallization is usually conducted in an autoclave so that the reaction mixture is subject to autogenous pressure.
- a suitable reactor vessel such as polypropylene jars or Teflon-lined or stainless-steel autoclaves
- the solid product is recovered from the reaction mixture by standard mechanical separation techniques such as centrifugation or filtration.
- the recovered solids are then rinsed with deionized water, and dried at an elevated temperature (e.g., 75° C. to 150° C.) for several hours (e.g., about 4 to 24 hours).
- the drying step can be performed under vacuum or at atmospheric pressure.
- the recovered crystalline molecular sieve product contains within its pore structure at least a portion of the structure directing agent used in its synthesis.
- the as-synthesized molecular sieve may be subjected to treatment to remove part or all of the structure directing agent used in its synthesis. Removal of the structure directing agent may be carried out by thermal treatment (e.g., calcination) in which the as-synthesized molecular sieve is heated at a temperature sufficient to remove part or all of the structure directing agent. While sub-atmospheric pressure may be used for the thermal treatment, atmospheric pressure is desired for reasons of convenience.
- the thermal treatment may be performed at a temperature at least 370° C. for at least a minute and generally not longer than 20 hours (e.g., from 1 to 12 hours).
- the thermal treatment can be performed at a temperature of up to 925° C. For example, the thermal treatment may be conducted at a temperature of 400° C. to 600° C. in the presence of an oxygen-containing gas. Additionally or alternatively, the structure directing agent may be removed by treatment with ozone.
- Any extra-framework metal cations in the molecular sieve can be replaced in accordance with techniques well known in the art (e.g., by ion exchange) with other cations.
- Replacing cations can include metal ions, hydrogen ions, hydrogen precursor (e.g., ammonium) ions, and mixtures thereof.
- Particularly preferred replacing cations are those which tailor the catalytic activity for certain organic conversion reactions. These include hydrogen, rare earth metals, and metals of Groups 2 to 15 of the Periodic Table of the Elements.
- molecular sieve SSZ-118 can have a chemical composition comprising the following molar relationship as described in Table 2:
- the as-synthesized form of the present molecular sieve may have molar ratios different from the molar ratios of reactants of the reaction mixture used to prepare the as-synthesized form. This result may occur due to incomplete incorporation of 100% of the reactants of the reaction mixture into the crystals formed (from the reaction mixture).
- molecular sieve SSZ-118 can have a chemical composition comprising the following molar relationship: Al 2 O 3 :( n )SiO 2 wherein n is at least 20 to 100 (e.g., 30 to 70, 35 to 60, or 40 to 50).
- the novel molecular sieve structure SSZ-118 is characterized by a powder XRD pattern which, in the as-synthesized form of the molecular sieve, includes at least the peaks set forth in Table 3 and which, in the calcined form of the molecular sieve, includes at least the peaks set forth in Table 4.
- the powder XRD patterns provided herein are based on a relative intensity scale in which the strongest line in the X-ray diffraction pattern is assigned a value of 100, where the corresponding relative intensities are: w (weak) is ⁇ 20; m (medium) is >20 to ⁇ 40; s (strong) is >40 to ⁇ 60; and vs (very strong) is >60.
- w weak
- m medium
- s strong
- vs very strong
- this line can be described as being a combination of two ranges. For example, a line with an intensity of 18 is at the upper end of a weak range, but a small variation could result in the intensity being in the range of about 20-25. In this case, the intensity range could be reported as being w-m.
- the powder X-ray diffraction patterns presented herein were collected by standard techniques.
- the radiation was CuK ⁇ radiation.
- the peak heights and the positions, as a function of 2 ⁇ where ⁇ is the Bragg angle, were read from the relative intensities of the peaks (adjusting for background), and d, the interplanar spacing corresponding to the recorded lines, can be calculated.
- Molecular sieve SSZ-118 may be used as a sorbent or as a catalyst to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance.
- Examples of organic conversion processes which may be catalyzed by SSZ-118 may include cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- SSZ-118 with another material resistant to the temperatures and other conditions employed in organic conversion processes.
- materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina.
- the latter may be either naturally occurring, or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides.
- Use of a material in conjunction with SSZ-118 i.e., combined therewith or present during synthesis of the new material which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes.
- Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction.
- These materials may be incorporated into naturally occurring clays (e.g., bentonite and kaolin) to improve the crush strength of the catalyst under commercial operating conditions.
- These materials i.e., clays, oxides, etc.
- These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
- Naturally occurring clays which can be composited with SSZ-118 include the montmorillonite and kaolin family, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with SSZ-118 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
- SSZ-118 can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- the relative proportions of SSZ-118 and inorganic oxide matrix may vary widely, with the SSZ-118 content ranging from 1 to 90 wt. % (e.g., 2 to 80 wt. %) of the composite.
- the resulting product was analyzed by powder XRD and SEM.
- the powder XRD pattern of the product is shown in FIG. 1 and indicates that the product is a new phase, designated SSZ-118.
- a SEM image of the product image is shown in FIG. 2 and indicates a uniform field of crystals.
- the peak broadening seen in the XRD pattern is due to disorder in the SSZ-118 crystal structure rather than to small crystal size.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 45.9, according to Inductively Coupled Plasma (ICP) elemental analysis.
- ICP Inductively Coupled Plasma
- the as-synthesized product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 49.6, according to ICP elemental analysis.
- the resulting product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 41.7, according to ICP elemental analysis.
- the resulting product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 48.5, according to ICP elemental analysis.
- Example 2 was repeated except that no additional deionized water was added in the synthesis gel.
- the H 2 O/SiO 2 molar ratio of the reaction mixture in this Example is 15, whereas the H 2 O/SiO 2 molar ratio of the reaction mixture in Example 2 is 25.
- the autoclave was put in an oven heated at 160° C. for 7 days with tumbling at 43 rpm.
- the solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- the resulting product was identified by powder XRD and SEM as a pure Beta zeolite.
- the powder XRD pattern of the product is shown in FIG. 1 .
- the as-synthesized product was identified by powder XRD and SEM as a pure SSZ-74 zeolite. This example shows that crystallizing a reaction mixture having a SiO 2 /Al 2 O 3 molar ratio greater than 100 produces SSZ-74 rather than SSZ-118.
- the as-synthesized molecular sieve product from example 1 was calcined inside a muffle furnace under a flow of air heated to 540° C. at a rate of 1° C./minute and held at 540° C. for 5 hours, cooled and then analyzed by powder XRD.
- the powder XRD pattern of the calcined material is shown in FIG. 1 and indicates that the material remains stable after calcination to remove the structure directing agent.
- Example 7 The calcined material from Example 7 was treated with 10 mL (per g of molecular sieve) of a 1 N ammonium nitrate solution at 95° C. for 2 hours. The solution was cooled, decanted off and the same process repeated.
- the product (NH 4 -SSZ-118) after drying was subjected to a micropore volume analysis using nitrogen as adsorbate and via the B.E.T. method.
- the molecular sieve exhibited a micropore volume of 0.20 cm 3 /g.
- the product (NH 4 -SSZ-118) after drying was subjected to a micropore size analysis using argon as adsorbate and via the DFT (density-function theory) method.
- the molecular sieve exhibited a micropore size of 5.6 ⁇ , indicating that SSZ-118 likely contains a medium-pore system.
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Abstract
A novel synthetic crystalline molecular sieve material, designated SSZ-118, is provided. SSZ-118 can be synthesized using 1,6-bis(N-methylpyrrolidinium)hexane dications as a structure directing agent. SSZ-118 may be used in organic compound conversion and/or sorptive processes.
Description
This application claims priority to and the benefit of U.S. Provisional Application Ser. No. 62/879,609, filed Jul. 29, 2019.
This disclosure relates to a novel synthetic crystalline molecular sieve designated SSZ-118, its synthesis, and its use in organic compound conversion and sorption processes.
Molecular sieves are a commercially important class of materials that have distinct crystal structures with defined pore structures that are shown by distinct X-ray diffraction (XRD) patterns and have specific chemical compositions. The crystal structure defines cavities and pores that are characteristic of the specific type of molecular sieve.
According to the present disclosure, a new crystalline molecular sieve, designated SSZ-118 and having a unique powder X-ray diffraction pattern, has now been synthesized using 1,6-bis(N-methylpyrrolidinium)hexane dications as a structure directing agent.
In one aspect, there is provided a molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including the following peaks:
2-Theta [°] | d-Spacing [Å] | Relative Intensity |
7.54 ± 0.30 | 11.28-12.21 | s-vs |
22.91 ± 0.30 | 3.83-3.93 | s-vs |
In its as-synthesized and anhydrous form, the molecular sieve can have a chemical composition comprising the following molar relationship:
Broadest | Secondary | |||
SiO2/Al2O3 | 20 to 100 | 30 to 70 | ||
Q/SiO2 | >0 to 0.1 | >0 to 0.1 | ||
M/SiO2 | >0 to 0.1 | >0 to 0.1 | ||
wherein Q comprises 1,6-bis(N-methylpyrrolidinium)hexane dications and M is a Group 1 or Group 2 metal.
In another aspect, there is provided a molecular sieve having, in its calcined form, a powder X-ray diffraction pattern including the following peaks:
2-Theta [°] | d-Spacing [Å] | Relative Intensity |
7.54 ± 0.30 | 11.28-12.21 | s-vs |
22.91 ± 0.30 | 3.83-3.93 | s-vs |
In its calcined form, the molecular sieve can have a chemical composition comprising the following molar relationship:
Al2O3:(n)SiO2
wherein n is in a range of from 20 to 100.
Al2O3:(n)SiO2
wherein n is in a range of from 20 to 100.
In a further aspect, there is provided a method of synthesizing the molecular sieve described herein, the method comprising (a) providing a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
In yet a further aspect, there is provided a process of converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising the molecular sieve described herein.
The term “as-synthesized” is employed herein to refer to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
The term “anhydrous” is employed herein to refer to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chem. Eng. News 1985, 63(5), 26-27.
Synthesis of the Molecular Sieve
Molecular sieve SSZ-118 can be synthesized by: (a) providing a reaction mixture comprising (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 or Group 2 metal (M); (4) a structure directing agent (Q) comprising 1,6-bis(N-methylpyrrolidinium)hexane dications; (5) a source of hydroxide ions; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
The reaction mixture can have a composition, in terms of molar ratios, within the ranges set forth in Table 1:
TABLE 1 | ||||
Reactants | Broadest | Secondary | ||
SiO2/Al2O3 | 50 to 100 | 50 to 100 | ||
M/SiO2 | 0.05 to 0.50 | 0.25 to 0.40 | ||
Q/SiO2 | 0.05 to 0.30 | 0.05 to 0.15 | ||
OH/SiO2 | 0.40 to 0.70 | 0.45 to 0.60 | ||
H2O/ |
20 to 40 | 25 to 35 | ||
In some aspects, the reaction mixture can have a SiO2/Al2O3 molar ratio in a range of 60 to 80.
Suitable sources of silicon oxide can include colloidal silica, fumed silica, precipitated silica, alkali metal silicates and tetraalkyl orthosilicates.
Suitable sources of aluminum oxide can include hydrated alumina, aluminum hydroxide, alkali metal aluminates, aluminum alkoxides, and water-soluble aluminum salts (e.g., aluminum nitrate).
Combined sources of silicon oxide and aluminum oxide can additionally or alternatively be used and can include aluminosilicate zeolites (e.g., zeolite Y) and clays or treated clays (e.g., metakaolin).
Any M-containing compound not detrimental to crystallization process can be used. Sources of the Group 1 or Group 2 metal can include metal hydroxide, metal oxide, metal halide, metal sulfate, metal nitrate, metal carboxylate, and metal aluminate. As used herein, the phrase “Group 1 or Group 2 metal” does not mean the Group 1 metals and Group 2 metals are used in the alternative, but instead that one or more Group 1 metals can be used alone or in combination with one or more Group 2 metals and that one or more Group 2 metals can be used alone or in combination with one or more Group 1 metals. Preferred Group 1 or Group 2 metals include sodium, potassium, and combinations thereof.
The structure directing agent (Q) comprises 1,6-bis(N-methylpyrrolidinium)hexane dications, represented by the following structure (1):
Suitable sources of Q are the hydroxides and/or other salts of the diquaternary ammonium compound.
The reaction mixture may contain seeds of a crystalline material, such as SSZ-118 from a previous synthesis, in an amount of from 0.01 to 10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) of the reaction mixture. Seeding can be advantageous in decreasing the amount of time necessary for complete crystallization to occur. In addition, seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of SSZ-118 over any undesired phases.
It is noted that the reaction mixture components can be supplied by more than one source. Also, two or more reaction components can be provided by one source. The reaction mixture can be prepared either batchwise or continuously.
Crystallization and Post-Synthesis Treatment
Crystallization of the molecular sieve from the above reaction mixture can be carried out under either static, tumbled or stirred conditions in a suitable reactor vessel, such as polypropylene jars or Teflon-lined or stainless-steel autoclaves, at a temperature of from 125° C. to 200° C. (e.g., 150° C. to 180° C.) for a time sufficient for crystallization to occur at the temperature used (e.g., from 1 day to 14 days). Crystallization is usually conducted in an autoclave so that the reaction mixture is subject to autogenous pressure.
Once the molecular sieve crystals have formed, the solid product is recovered from the reaction mixture by standard mechanical separation techniques such as centrifugation or filtration. The recovered solids are then rinsed with deionized water, and dried at an elevated temperature (e.g., 75° C. to 150° C.) for several hours (e.g., about 4 to 24 hours). The drying step can be performed under vacuum or at atmospheric pressure.
As a result of the crystallization process, the recovered crystalline molecular sieve product contains within its pore structure at least a portion of the structure directing agent used in its synthesis.
The as-synthesized molecular sieve may be subjected to treatment to remove part or all of the structure directing agent used in its synthesis. Removal of the structure directing agent may be carried out by thermal treatment (e.g., calcination) in which the as-synthesized molecular sieve is heated at a temperature sufficient to remove part or all of the structure directing agent. While sub-atmospheric pressure may be used for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment may be performed at a temperature at least 370° C. for at least a minute and generally not longer than 20 hours (e.g., from 1 to 12 hours). The thermal treatment can be performed at a temperature of up to 925° C. For example, the thermal treatment may be conducted at a temperature of 400° C. to 600° C. in the presence of an oxygen-containing gas. Additionally or alternatively, the structure directing agent may be removed by treatment with ozone.
Any extra-framework metal cations in the molecular sieve can be replaced in accordance with techniques well known in the art (e.g., by ion exchange) with other cations. Replacing cations can include metal ions, hydrogen ions, hydrogen precursor (e.g., ammonium) ions, and mixtures thereof. Particularly preferred replacing cations are those which tailor the catalytic activity for certain organic conversion reactions. These include hydrogen, rare earth metals, and metals of Groups 2 to 15 of the Periodic Table of the Elements.
Characterization of the Molecular Sieve
In its as-synthesized and anhydrous form, molecular sieve SSZ-118 can have a chemical composition comprising the following molar relationship as described in Table 2:
TABLE 2 | ||||
Broadest | Secondary | |||
SiO2/Al2O3 | 20 to 100 | 30 to 70 | ||
Q/SiO2 | >0 to 0.1 | >0 to 0.1 | ||
M/SiO2 | >0 to 0.1 | >0 to 0.1 | ||
wherein compositional variables Q and M are as described herein above.
It should be noted that the as-synthesized form of the present molecular sieve may have molar ratios different from the molar ratios of reactants of the reaction mixture used to prepare the as-synthesized form. This result may occur due to incomplete incorporation of 100% of the reactants of the reaction mixture into the crystals formed (from the reaction mixture).
In its calcined form, molecular sieve SSZ-118 can have a chemical composition comprising the following molar relationship:
Al2O3:(n)SiO2
wherein n is at least 20 to 100 (e.g., 30 to 70, 35 to 60, or 40 to 50).
Al2O3:(n)SiO2
wherein n is at least 20 to 100 (e.g., 30 to 70, 35 to 60, or 40 to 50).
The novel molecular sieve structure SSZ-118 is characterized by a powder XRD pattern which, in the as-synthesized form of the molecular sieve, includes at least the peaks set forth in Table 3 and which, in the calcined form of the molecular sieve, includes at least the peaks set forth in Table 4.
TABLE 3 |
Characteristic Peaks for As-Synthesized SSZ-118 |
2-Theta [°] | d-Spacing [Å] | Relative Intensity |
7.54 ± 0.30 | 11.28-12.21 | s-vs |
22.91 ± 0.30 | 3.83-3.93 | s-vs |
TABLE 4 |
Characteristic Peaks for Calcined SSZ-118 |
2-Theta [°] | d-Spacing [Å] | Relative Intensity |
7.54 ± 0.30 | 11.28-12.21 | s-vs |
22.91 ± 0.30 | 3.83-3.93 | s-vs |
The powder XRD patterns provided herein are based on a relative intensity scale in which the strongest line in the X-ray diffraction pattern is assigned a value of 100, where the corresponding relative intensities are: w (weak) is ≤20; m (medium) is >20 to ≥40; s (strong) is >40 to ≤60; and vs (very strong) is >60. When a characteristic line is present near an end point for one of these ranges, variations in the intensity of the line due to various known experimental factors, including the presence of impurities and the instrument used, can result in the intensity being in the adjacent range. Therefore, this line can be described as being a combination of two ranges. For example, a line with an intensity of 18 is at the upper end of a weak range, but a small variation could result in the intensity being in the range of about 20-25. In this case, the intensity range could be reported as being w-m.
The powder X-ray diffraction patterns presented herein were collected by standard techniques. The radiation was CuKα radiation. The peak heights and the positions, as a function of 2θ where θ is the Bragg angle, were read from the relative intensities of the peaks (adjusting for background), and d, the interplanar spacing corresponding to the recorded lines, can be calculated.
Sorption and Catalysis
Molecular sieve SSZ-118 may be used as a sorbent or as a catalyst to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by SSZ-118, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity. Examples of organic conversion processes which may be catalyzed by SSZ-118 may include cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
As in the case of many catalysts, it may be desirable to incorporate SSZ-118 with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring, or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. Use of a material in conjunction with SSZ-118 (i.e., combined therewith or present during synthesis of the new material) which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays (e.g., bentonite and kaolin) to improve the crush strength of the catalyst under commercial operating conditions. These materials (i.e., clays, oxides, etc.) function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays which can be composited with SSZ-118 include the montmorillonite and kaolin family, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with SSZ-118 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
In addition to the foregoing materials, SSZ-118 can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
The relative proportions of SSZ-118 and inorganic oxide matrix may vary widely, with the SSZ-118 content ranging from 1 to 90 wt. % (e.g., 2 to 80 wt. %) of the composite.
The following illustrative examples are intended to be non-limiting.
1.30 g of deionized water, 0.28 g of a 45% KOH solution, 1.08 g of a 20% 1,6-bis(N-methylpyrrolidinium)hexane hydroxide solution (SACHEM, Inc.), 0.02 g of 50% Reheis F-2000 aluminum hydroxide dried gel and 1.50 g of LUDOX© AS-30 colloidal silica (30 wt. % suspension in water) were mixed together in a Teflon liner. The gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 160° C. for 7 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The resulting product was analyzed by powder XRD and SEM. The powder XRD pattern of the product is shown in FIG. 1 and indicates that the product is a new phase, designated SSZ-118. A SEM image of the product image is shown in FIG. 2 and indicates a uniform field of crystals.
It is believed that the peak broadening seen in the XRD pattern is due to disorder in the SSZ-118 crystal structure rather than to small crystal size.
The product had a SiO2/Al2O3 molar ratio of 45.9, according to Inductively Coupled Plasma (ICP) elemental analysis.
1.82 g of deionized water, 0.24 g of a 50% NaOH solution, 1.44 g of a 20% 1,6-bis(N-methylpyrrolidinium)hexane hydroxide solution, 0.02 g of 50% Reheis F-2000 aluminum hydroxide dried gel and 2.00 g of LUDOX© AS-30 colloidal silica were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 160° C. for 7 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The as-synthesized product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
The product had a SiO2/Al2O3 molar ratio of 49.6, according to ICP elemental analysis.
4.08 g of deionized water, 0.13 g of a 50% NaOH solution, 1.16 g of a 20% 1,6-bis(N-methylpyrrolidinium)hexane hydroxide solution and 0.50 g of CBV760 Y-zeolite powder (Zeolyst International, SiO2/Al2O3 molar ratio=60) were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 170° C. for 7 days under static conditions. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The resulting product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
The product had a SiO2/Al2O3 molar ratio of 41.7, according to ICP elemental analysis.
8.14 g of deionized water, 0.32 g of a 50% NaOH solution, 2.32 g of a 20% 1,6-bis(N-methylpyrrolidinium)hexane hydroxide solution and 1.00 g of CBV780 Y-zeolite powder (Zeolyst International, SiO2/Al2O3 molar ratio=80) were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 170° C. for 7 days under static conditions. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The resulting product was identified by powder XRD and SEM as a pure aluminosilicate SSZ-118 molecular sieve.
The product had a SiO2/Al2O3 molar ratio of 48.5, according to ICP elemental analysis.
Example 2 was repeated except that no additional deionized water was added in the synthesis gel. The H2O/SiO2 molar ratio of the reaction mixture in this Example is 15, whereas the H2O/SiO2 molar ratio of the reaction mixture in Example 2 is 25. The autoclave was put in an oven heated at 160° C. for 7 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The resulting product was identified by powder XRD and SEM as a pure Beta zeolite. The powder XRD pattern of the product is shown in FIG. 1 .
1.82 g of deionized water, 0.24 g of a 50% NaOH solution, 1.44 g of a 20% 1,6-bis(N-methylpyrrolidinium)hexane hydroxide solution, 0.01 g of 50% Reheis F-2000 aluminum hydroxide dried gel and 2.00 g of LUDOX© AS-30 colloidal silica were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 160° C. for 7 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
The as-synthesized product was identified by powder XRD and SEM as a pure SSZ-74 zeolite. This example shows that crystallizing a reaction mixture having a SiO2/Al2O3 molar ratio greater than 100 produces SSZ-74 rather than SSZ-118.
The as-synthesized molecular sieve product from example 1 was calcined inside a muffle furnace under a flow of air heated to 540° C. at a rate of 1° C./minute and held at 540° C. for 5 hours, cooled and then analyzed by powder XRD. The powder XRD pattern of the calcined material is shown in FIG. 1 and indicates that the material remains stable after calcination to remove the structure directing agent.
The calcined material from Example 7 was treated with 10 mL (per g of molecular sieve) of a 1 N ammonium nitrate solution at 95° C. for 2 hours. The solution was cooled, decanted off and the same process repeated.
The product (NH4-SSZ-118) after drying was subjected to a micropore volume analysis using nitrogen as adsorbate and via the B.E.T. method. The molecular sieve exhibited a micropore volume of 0.20 cm3/g.
The product (NH4-SSZ-118) after drying was subjected to a micropore size analysis using argon as adsorbate and via the DFT (density-function theory) method. The molecular sieve exhibited a micropore size of 5.6 Å, indicating that SSZ-118 likely contains a medium-pore system.
Claims (7)
1. A molecular sieve having, in its calcined form, a powder X-ray diffraction pattern consisting of the following peaks:
2. The molecular sieve of claim 1 , and having a composition comprising the molar relationship:
Al2O3:(n)SiO2
Al2O3:(n)SiO2
wherein n is in a range of 20 to 100.
3. The molecular sieve of claim 1 , and having a composition comprising the molar relationship:
Al2O3:(n)SiO2
Al2O3:(n)SiO2
wherein n is in a range of 30 to 70.
4. A process for converting a feedstock comprising an organic compound to a conversion product, the process comprising contacting the feedstock at organic compound conversion conditions with a catalyst comprising the molecular sieve of claim 1 .
5. A molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern consisting of the following peaks:
6. The molecular sieve of claim 5 , having a chemical composition comprising the following molar relationship:
wherein Q comprises 1,6-bis(N-methylpyrrolidinium)hexane dications and M is a Group 1 or Group 2 metal.
7. The molecular sieve of claim 5 , having a chemical composition comprising the following molar relationship:
wherein Q comprises 1,6-bis(N-methylpyrrolidinium)hexane dications and M is a Group 1 or Group 2 metal.
Priority Applications (1)
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KR20220042386A (en) | 2022-04-05 |
CN114258386A (en) | 2022-03-29 |
JP7417711B2 (en) | 2024-01-18 |
EP4003913A1 (en) | 2022-06-01 |
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